US3855318A - Selective methylation of phenols - Google Patents

Selective methylation of phenols Download PDF

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US3855318A
US3855318A US00207546A US20754671A US3855318A US 3855318 A US3855318 A US 3855318A US 00207546 A US00207546 A US 00207546A US 20754671 A US20754671 A US 20754671A US 3855318 A US3855318 A US 3855318A
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catalyst
phenol
vanadium
methanol
cresol
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H Nakajima
F Nomura
S Iszwa
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom

Definitions

  • ABSTRACT Vapor phase methylation of phenols with methanol in contact with a vanadium oxide catalyst which may additionally contain iron oxide and at least one other oxide of magnesium, titanium, manganese, beryllium 0r boron.
  • This invention relates to a catalytic process for the methylation of the ortho position of phenols having at least one ortho hydrogen and to certain novel catalysts useful in the process.
  • each R is a monovalent substituent selected from the group consisting of hydrogen, methyl, phenyl, and methyl substituted phenyl.
  • British Pat. No. 717,588 relates to an alkylation process in which a metal oxide having dehydrating action such as the oxides of aluminum, thorium, zirconium, zinc, iron, manganese, magnesium or calcium are employed as catalysts.
  • a metal oxide having dehydrating action such as the oxides of aluminum, thorium, zirconium, zinc, iron, manganese, magnesium or calcium are employed as catalysts.
  • the process is not completely satisfactory, however, because it is not sufficiently selective.
  • the methyla-of phenol leads not only to the desired ortho-substituted products but also to undesirably large amounts of the meta and para isomers.
  • the separation of the undesired byproducts is complicated and expensive, but they must be separated especially if the desired product, 2,6-xyleno1 is to be used for the production of polyphenylene oxide.
  • a further feature of the invention is the discovery that the addition of water vapor to the reaction system in the amount of from about 2 to 12 mols per mol of the phenol utilized helps to prevent the catalysts from breaking down into finer particles or powders which clog the reactor. Thus the life of the catalyst is extended, and the periods between shut downs of the operation to clean the reactor are prolonged.
  • oxide as used in association with various metals in describing and claiming this invention refers to all of the several oxides of the metal known to exist such as V 0 V 0 V 0 VO, Fe O FY2 0 FeO, MgO, TiO MnO MnO, Mn O and to mixtures of these various oxides.
  • the bimetallic vanadium-iron catalysts used in this invention the atomic ratio of iron to vanadium is normally from about 9 to l /9.
  • the preferred range for optimum results is from 4 to H4.
  • the atomic ratio of vanadium to iron to other metal or mixture of metals is from about 1/9 9 1 z 1 0.01.
  • the preferred range in polymetallic catalysts is l/44:1:l-O.l.
  • Vanadium and any of the other metals used in the present invention may be obtained from any of their usual compounds such as nitrates, hydroxides, carbonates, oxalates, halides, and the like. They may be converted to the desired oxides by immersing, mixing, coprecipitation or other conventional methods. The methods for preparing the catalysts are illustrated in the examples. In actual use they may be supported on suitable carrers such as alumina, silica, silica-alumina, and the like.
  • a mixture of methanol and the selected phenol is contacted with the catalyst in the vapor phase at an elevated temperature to methylate the phenol at one or both of the ortho positions.
  • a mixture of methanol and phenol for example, can be converted predominantly to ortho cresol or to 2,6-xylenol, or to a mixture of these compounds.
  • Phenols which may be methylated by the process of this invention include, for example, phenol itself, 0- cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5- xylenol, 3,5-xylenol, 2,3,4-trimethylphenol, 2,3,5- trimethylphenol, 3,4,5-trimethylphenol, 2,3,4,5- tetramethylphenol, O-phenylphenol, p-phenylphenol, 2-tolylphenol, 2,4-diphenylphenol, 2,3- diphenylphenol, 2-xylylphenol, 2-mesitylphenol, 2- durylphenol, 2-phenyl-4-methylphenol, 2-tolyl-4- phenylphenol, 2-phenyl-4-tolylphenol or S-methyl- Sphenylphenol. All of these phenols may be represented by the formula wherein each R is a nonvalent substituent selected from the group consisting of hydrogen, methyl, pheny
  • Any one or a mixture of the above phenols is vaporized together with methanol and passed through a reactor containing the selected catalyst.
  • the reactor may take any of the usual forms such as stationary bed, moving bed, fluidized bed, and the like.
  • the reaction temperature is typically in the range of from about 250C. to 450C., with the preferred range being from 300C. to 400C. At temperatures appreciably lower than 250C. there is a noticeable decrease in yield, and as the temperature increases much above 500C. there is an appreciable increase in the amount of byproducts produced, especially byproducts which are methylated in positions other than the ortho position. There is also a noticeably increase in decomposition of methanol.
  • a particular advantage of the process of this invention is that it can be carried out at a relatively low temperature compared to known methods so that the cost of operation is decreased. Additionally there is less decomposition of starting materials or products, and the catalyst life is markedly increased.
  • methylation is effected even with small amounts of methanol
  • the molar ratio of methanol to phenol type reactant is from about 1:1 to :1.
  • a reaction inert gas such as nitrogen, hydrogen, carbon monoxide, carbon dioxide or methane is often helpful.
  • a reaction inert gas such as nitrogen, hydrogen, carbon monoxide, carbon dioxide or methane is often helpful.
  • water vapor helps to extend the life of the catalyst even longer than usual.
  • it may be employed in a water vapor-phenol reactant mole ratio of from about 2:1 to 12:1.
  • the amount of water vapor is lower than about 2 mols per mol of phenol the effect on ex tending catalyst life is decreased.
  • the ratio increased appreciably above 12:1 the partial pressure of the phenol decreases and this in turm reduces the space-time yield of methylated products.
  • reaction pressure is not critical. It may be carried out at atmospheric pressure, and may also be carried out over a wide range of pressure varying from about 0.5 to 50 atmospheres.
  • Best catalytic activity and optimum selectivity is achieved by maintaining the gas space velocity at from about 360 to 18,000 hr".
  • the preferred range from the viewpoint of economical operation is 900 to 12,000 hr".
  • the gas space velocity will be on the high side of the range at higher temperatures and will be decreases as the operating temperature decreases.
  • the pressure loss represented by AP is the differential pressure across the ends of the catalyst layers. It is measured with a manometer.
  • EXAMPLE 1 Preparation of Catalyst Twenty g. of ammonium metavanadate and 5 g. of oxalic acid are dissolved in 40 cc. of pure water and heated over a boiling water bath to dryness. The dried mass is then heated at 550C. for three hours in an air stream. The resultant material is ground to 16 32 mesh particles and used as the catalyst.
  • a mixture of methanol and phenol in the molar proportion 5 l and nitrogen gas are continuously supplied at a rate 7.9 cc/hr. and 17.7 cc/min. respectively through a preheater maintained at 220C. in which the feed is vaporized, to a pyrex glass reactor having a 1.8 cm internal diameter containing 1.2 cc. of the catalyst.
  • the reactor is uniformly maintained at 350C.
  • the reaction is carried out for 50 hours with the gas space velocity of the feed controlled at 9,000 hrs.
  • the resultant product is gas-liquid separated by means of air-cooled traps and dry-ice traps (-78C.). Gas and liquid are individually analyzed with gas chromatography. According to the analysis, the conversion of phenol was 50.5percent and the yield of o-cresol and 2,6-xylenol were 62.1percent and 28.4percent respectively based on the phenol converted.
  • Example 1 is repeated to methylate o-cresol with methanol except that the molar ratio of methanol to ocresol and methanol to o-cresol to water in each feed is 3 1 and 3 z 1 z 3, respectively. The results are shown in Table 2.
  • the resultant particles are pulverized to the size of 16-32 mesh and used as the catalyst.
  • the atomic ratio of iron to vanadium in the thus prepared catalyst is 2:1, the total amount of vanadium pentoxide and ferric oxide as carried on aluminum oxide being 10 percent by weight based on aluminum oxide.
  • the dried mass is sieved to give 16-32 mesh particles, which are then heated at 450C. for three hours while air is passed over them to give the catalyst.
  • the atomic ratio of iron to vanadium of the catalyst is l 1.
  • Other catalysts having various atomic ratios are prepared in the same manner.
  • Reaction Example 1 is repeated using seven different catalysts prepared in accordance with the example. The results are shown in Table 3.
  • Example 17-20 Preparation of Catalyst
  • ferric nitrate is dissolved in 200 cc. of pure water, and 94 cc. of 14 percent aqueous ammonia added dropwise to the resultant solution until the pH of the solution reaches 6.8.
  • the precipitate which forms is washed with water and filtered.
  • Twenty five g. of the thus obtained precipitate is added to 50 cc. of an aqueous solution of ammonium metavanadate.
  • the resultant solution is concentrated to dryness over a hot water bath.
  • the dried mass is sieved to 16-1- 6-32 mesh particles, which are heated at 650C. for three hours under passing air to give the catalyst.
  • the atomic ratio of iron to vanadium in the catalyst is l 1.
  • Other catalysts of various atomic ratios are prepared in the similar manner.
  • Example 17 is run on a mixture of methanol with phenol in the molar ratio of 5 1, while Examples 18-22, are run on a mixture of methanol, phenol and water in the molar ratio of 5 1 z 3, respectively.
  • the results measured after passage of reaction hours are shown in Table EXAMPLE 23
  • Preparation of Catalyst In 100 cc. of pure water, there are dissolved 7.8 g. of vanadium trichloride and 10.0 g. of ferric nitrate. Then, 18 cc. of 14 percent aqueous ammonia are added dropwise to the resultant solution until the pH of the solution increases to 6.8. The precipitate formed is then washed with water, filtered and dried at l 10C. fo 24 hours. The dried material is heated at 650C. for three hours in the air stream to give ghe catalyst.
  • the atomic ratio of iron to vanadium of the catalyst is 0.5 1.
  • reaction is carried out on a mixed feed of methanol, phenol and water in the molar proportion of 8 l 6, using 2 cc. of the catalyst.
  • the mixture feed is supplied to the reactor at a rate of 7.9 cc./hr.
  • the procedure is similar to Example 1, but the nitrogen carrier gas is omitted.
  • Reaction Example 1 is repeated using 2 cc. of catalyst for each run on the feed of various compositions.
  • the feed is supplied at a rate of 7.9 cc./hr. at a room temperature.
  • EXAMPLE 35 Preparation of Catalyst An aqueous solution prepared by dissolving 69.1 g. of ferric nitrate in 150 cc. of pure water is added with stirring to an aqueous solution of 20.0 g. of ammonium metavanadate and 6 g. of oxalic acid dissolved in 150 cc. of pure water. To the resultant solution there is added dropwise 55 cc. of 14 percent aqueous ammonia until the pH of the solution increases to 6.8. The precipitate which forms is washed with water, filtered, dried for 24 hours at 1 C. and further heated for another three hours in an air stream, to give the catalyst. The atomic ratio of iron to vanadium of the catalyst is 1 1.
  • Reaction Example 1 is repeated for 600 hours on a feed mixture of methanol, phenol and water in the molar ratio of 8 l 6. The changes measured with the passage of reaction times are shown in Table 7.
  • EXAMPLE 36 Methylation of o-cresol with methanol is made in the presence of the catalyst as in Example 13 having an atomic ratio of iron to vanadium of 1:1.
  • Example 1 is repeated on the feed of which molar ratio of phenol to o-cresol is 3 l, to give o-cresol conversion of 95.8 percent and a yield of 2,6-xylenol bases on converted ocresol of 97.5 percent. Similar results are obtained when the nitrogen is replaced with methane.
  • EXAMPLE 37 O-cresol is methylated with methanol, using the catalyst as prepared in Example 24.
  • Example 1 is repeated on a feed containing methanol.
  • o-cresol and water in the proportion of 3 l 3.
  • AP reaches 9.5 cm.
  • H O o-cresol conversion is 85.8% and the yield of 2,6-xylenol is 83.4 percent.
  • EXAMPLE 38 Methylation of phenol and o-cresol with methanol is made using the catalyst as prepared in Example 13.
  • Example l is repeated except that the molar ratio of methanol to phenol is 4 1 and phenol to O-cresol is 2 1.
  • An analysis of product liquid shows 12.4 percent of phenol, 24.1 percent of o-cresol and 61.4 percent of 2,6-xylenol.
  • EXAMPLE 39 Preparation of Catalyst In 130 cc. of water there are dissolved 25.0 g. of ferric nitrate (Fe(NO .9H O), 7.2 g. of ammonium metavanadate and 5 g. of oxalic acid. To the resultant solution there are added 20 cc. of an aqueous solution of 1.59 g. of magnesium nitrate (Mg(NO .6H O). The pH of the solution is increased to 6.8 by adding 32 cc. of 14 percent aqueous ammonia with stirring. The precipitate which forms is washed with water, filtered, dried at l 10C. for 24 hours and heated at 450C. for another three hours.
  • ferric nitrate Fe(NO .9H O)
  • Mg(NO .6H O magnesium nitrate
  • the pH of the solution is increased to 6.8 by adding 32 cc. of 14 percent aqueous ammonia with stirring.
  • the atomic ratio of iron to vanadium of the catalyst is 1, magnesium to iron is 0.1 1.
  • Another catalyst containing titanium oxide is prepared by repeating the above operation with titanium tetrachloride substituted for magnesium nitrate.
  • Anothe catalyst containing magnesium oxide and titanium oxide is prepared in a similar manner by adding magnesium nitrate and titanium tetrachloride.
  • Reaction Example 1 is repeated using catalysts as tabulated in Table 8.
  • EXAMPLE 48-54 Preparation of Catalyst In 150 cc. water there are dissolved 25.0 g. ferric nitrate, 7.2 g. of ammonium metavanadate, 5 g. oxalic acid and 4.67 g. manganese nitrate (Mn(NO .4H O). With stirring, 36 cc. of 14 percent aqueous ammonia is added dropwise until the pH of the solution increases to 6.8. The precipitate formed is washed with water, filtered, dried at 1 10C. for 24 hours, and heated at 450C. for another three hours, to give the catalyst. The atomic ratio of iron to vanadium of thus prepared catalyst is 1, and that of manganese to iron is 0.3 1.
  • the various atomic ratios in the catalyst are as follows: Fe/V l, Mg/Fe 0.1, Ti/Fe 0.1 and Mn/Fe 0.1.
  • Example 1 Reaction In each run, Example 1 is repeated using the catalyst prepared as above. Results are shown in Table 10.
  • EXAMPLE 69 Methylation is carried out for 1800 hours in succession using the catalyst as prepared in Example 62.
  • the composition of the catalyst is such that Fe/V l, Mg/Fe Ti/Fe 0.1, Mn/Fe 0.3.
  • Example 1 is repeated using 5 cc. of the catalyst on the feed having a methanol, phenol, water ratio of 8 l 6. Results are shown in Table 11.
  • EXAMPLE 71 Preparation of Catalyst Twenty five g. of ferric nitrate, 47.2 g. of ammonium metavanadate, and 5 g. of oxalic acid are dissolved in 150 cc. of water. To the resultant solution is added dropwise with stirring, 24 cc. of 14 percent aqueous ammonia until the pH of the solution reaches 6.8. The precipitate formed is washed with water, filtered, a solid lump is obtained. The lump is suspended in 50 cc. of water, to which 1.15 g. boric acid is added and the whole dried over a boiling water bath, dried at l C. for 24 hours and heated at 450C. for three hours. The atomic ratio of iron to vanadium is l 1, that of boron to iron being 0.3 1.
  • Reaction Example 1 is repeated using the thus prepated catalyst, giving 81.2 percent phenol conversion.
  • the yield of 2,6-xylenol based on phenol in the feed is 39.6 percent and the total yield of o-cresol plus 2,6-xylenol based on converted methanol is 49.6 percent.
  • EXAMPLE 72 Methylation of o-cresol with methanol is made in accordance with Example 1 using the same catalyst as prepared in Example 64 on a feed material containing methanol, o-cresol and water in a molar proportion of 3 l 3. One hundred and twenty hours of reaction gives 88.9 percent o-cresol conversion. The yield of 2,6-xylenol based on o-cresol in the feed material is 87.4 percent.
  • EXAMPLE 73 A mixture of phenol and o-cresol is methylated with methanol using 2 cc. of the same catalyst as prepared in Example 64, in accordance with Example I on a feed containing methanol, phenol, o-cresol and water in a molar proportion of 4 l 2 6. After 100 hours, AP reaches 3.6 cm H O. The composition of the liquid product as analyzed by a gas chromatography is 2.5 percent phenol, 13.9 percent o-cresol and 82.2 percent of 2,6-xylenol.
  • EXAMPLE 74 Preparation of Catalyst To 150 cc. of an aqueous solution of 10 percent oxalic acid is added 27 g. vanadium pentoxide, which is then dissolved by heating the mixture at C. The solution is concentrated to dryness over a boiling water bath and heated at 500C. for three hours under passing air, giving vanadium oxide which is used as the catalyst. Repetition of the experiment of Example I using this catalyst gives, after 48 hours of reaction, 45.8 percent phenol conversion. The yields of o-cresol and 2,6- xylenol based on converted phenol are 63.3 percent and 27.9 percent respectively. Similar results are obtained with 2-xylylphenol and 2-tolyl-4-phenylphenol.
  • EXAMPLE 75 Preparation of Catalyst To 150 cc. of a 10 percent oxalic acid aqueous solution is added 18 g. of vanadium pentoxide and 15.8 g. of ferric nitrate, which are then heated for dissolving. The resultant solution is concentrated to dryness over a boiling water bath. The dried material is heated at 500C. for three hours under passing air to give vanadium oxide catalyst. The atomic ratio of iron to vanadium of the catalyst is l 1.
  • Example 1 is repeated using the thus prepared catalyst to give, after 50 hours, 65.4 percent phenol conversion.
  • the yields of o-cresol based on converted phenol and that of 2,6-xylenol based on converted phenol are 66.8 percent and 30.2 percent, respectively.
  • Table 4 Yield Based on Phenol Total Yield of o-Cresol Example Atomic ratio of AP Phenol in Feed 1%) and 2,6-Xylenol Based No Catalyst (V/Fe) Water (cm Hp) Conversion o-Cresol 2.6-Xylenol on Converted Phenol 17 Ill 72.8 89.9 47.5 40.8 98.2 18 1/9 Added 4.3 67.3 37.3 21.9 88.1 19 1/2 do 6.0 90.2 51.7 37.1 98.6 20 1]! do 6.4 93.8 45.4 46.5 98.0 21 2/1 do 7.8 77.4 38.8 37.2 98.2 22 9/1 do 16.7 71.8 39.6 27.0 92.7
  • a process of methylating a phenol in the ortho position which comprises reacting methanol with a phenol having the formula 3.
  • reaction mixture contains from about 2 to 12 mols of water vapor per mol of phenol reactant.
  • a process as in claim 1 wherein the molar ratio of methanol to phenol reactant is from about 1 l to 10 l.
  • a process of methylating phenol in the ortho position which comprises reacting methanol with phenyl in the vapor phase in the presence of a vanadium oxide catalyst at a temperature of from about 250C. to 450C.
  • the catalyst is a metallic oxide containing iron and vanadium in the atomic ratio of from about 9 to H9.
  • the catalyst contains iron, vanadium, and at least one other metal selected from the group consisting of manganese, magnesium, titanium, beryllium and boron wherein the atomic ratio of vanadium to iron to other metal or mixture thereof is from about l/9-9: l l 0.01.
  • reaction mixture contains from about 2 to l2 mols of water vapor per mol of phenol.
  • a process as in claim 7 wherein the molar ratio of methanol to phenol is from about 1 l to 10 l.
  • a process as in claim 7 wherein the temperature is from 300C. to 400C.
  • a process of methylating o-cresol in the ortho position which comprises reacting methanol with o-eresol in the vapor phase in the presence of a vanadium oxide catalyst at a temperature of from about 250C. to 450C 14.
  • the catalyst contains iron, vanadium, and at least one other metal selected from the group consisting of manganese, magnesium, titanium, beryllium and boron wherein the atomic ratio of vanadium to iron to other metal or mixture thereof is from about l/9-9: l l 0.0].
  • reaction mixture contains from about 2 to l2 c8 mols of water vapor per mol of o-cresol.
  • a process as in claim 13 wherein the molar ratio of methanol to o-cresol is from about I l to 10 1 l.

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971832A (en) * 1970-07-17 1976-07-27 Mitsubishi Petrochemical Company Limited Process for producing ortho-methylphenols
JPS5663932A (en) * 1979-10-29 1981-05-30 Mitsui Toatsu Chem Inc Preparation of selectively ortho-alkylated phenol compound
US4329517A (en) * 1979-05-16 1982-05-11 Mitsui Petrochemical Industries Ltd. Process for production of mono- or di-ortho-methyl-substituted phenols by catalytic methylation and catalyst therefor
US4400557A (en) * 1981-02-04 1983-08-23 Braunkohlen Kraftstoff Aktiengesellschaft Process for the o-substitution of phenols
US4517389A (en) * 1982-08-10 1985-05-14 Asahi Kasei Kogyo Kabushiki Kaisha Process for methylating the ortho position of a phenol
US5371306A (en) * 1992-12-31 1994-12-06 Korea Advanced Institute Of Science And Technology Modified magnesium oxide catalyst
US6593501B2 (en) * 2000-09-18 2003-07-15 Asahi Kasei Kabushiki Kaisha Process for the preparation of 2,6-xylenol
US9012697B2 (en) 2011-03-08 2015-04-21 Elantas Gmbh Process for preparing alkylated hydroxyaromatics in microreactors

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2756461C2 (de) * 1977-12-17 1984-10-31 Rütgerswerke AG, 6000 Frankfurt Verfahren zur Herstellung von Mono-o-alkylphenolen
AU2003260344A1 (en) * 2002-08-02 2004-02-25 Vanetta S.P.A. Redox process particularly for the production of menadione and use of polyoxometalates
CN118949985A (zh) * 2024-07-26 2024-11-15 天津大学 一种铁氧化物催化剂、酚和甲醇甲基化制备2,6-二甲酚联产邻甲酚催化剂的方法和应用

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US2091483A (en) * 1934-11-02 1937-08-31 Sharples Solvents Corp Manufacture of secondary and tertiary alkyl phenols
US2435087A (en) * 1943-03-19 1948-01-27 Shell Dev Process for the separation of mixtures of alkyl phenols through selective alkylation
US2910515A (en) * 1958-10-24 1959-10-27 Universal Oil Prod Co Alkylation of aromatic compounds
BE603254A (fr) * 1960-05-04 1961-09-01 Bayer Ag Procédé de préparation de composés hydroxyaromatique alkylés
US3479410A (en) * 1967-05-18 1969-11-18 Gen Electric Selective vapor phase methylation of phenols
US3642912A (en) * 1967-12-11 1972-02-15 Coal Tar Research Ass The Alkylation of phenols

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091483A (en) * 1934-11-02 1937-08-31 Sharples Solvents Corp Manufacture of secondary and tertiary alkyl phenols
US2435087A (en) * 1943-03-19 1948-01-27 Shell Dev Process for the separation of mixtures of alkyl phenols through selective alkylation
US2910515A (en) * 1958-10-24 1959-10-27 Universal Oil Prod Co Alkylation of aromatic compounds
BE603254A (fr) * 1960-05-04 1961-09-01 Bayer Ag Procédé de préparation de composés hydroxyaromatique alkylés
US3479410A (en) * 1967-05-18 1969-11-18 Gen Electric Selective vapor phase methylation of phenols
US3642912A (en) * 1967-12-11 1972-02-15 Coal Tar Research Ass The Alkylation of phenols

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971832A (en) * 1970-07-17 1976-07-27 Mitsubishi Petrochemical Company Limited Process for producing ortho-methylphenols
US4329517A (en) * 1979-05-16 1982-05-11 Mitsui Petrochemical Industries Ltd. Process for production of mono- or di-ortho-methyl-substituted phenols by catalytic methylation and catalyst therefor
JPS5663932A (en) * 1979-10-29 1981-05-30 Mitsui Toatsu Chem Inc Preparation of selectively ortho-alkylated phenol compound
US4400557A (en) * 1981-02-04 1983-08-23 Braunkohlen Kraftstoff Aktiengesellschaft Process for the o-substitution of phenols
US4517389A (en) * 1982-08-10 1985-05-14 Asahi Kasei Kogyo Kabushiki Kaisha Process for methylating the ortho position of a phenol
US5371306A (en) * 1992-12-31 1994-12-06 Korea Advanced Institute Of Science And Technology Modified magnesium oxide catalyst
US6593501B2 (en) * 2000-09-18 2003-07-15 Asahi Kasei Kabushiki Kaisha Process for the preparation of 2,6-xylenol
US9012697B2 (en) 2011-03-08 2015-04-21 Elantas Gmbh Process for preparing alkylated hydroxyaromatics in microreactors

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DE2161252B2 (de) 1974-02-21
DE2161252C3 (de) 1974-10-03
IT943869B (it) 1973-04-10
DE2161252A1 (de) 1972-06-29
FR2117674A5 (enExample) 1972-07-21
GB1378179A (en) 1974-12-27
GB1378180A (en) 1974-12-27

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